WO2014142024A1 - Composition de résine époxy, pré-imprégné, et matériau composite renforcé par fibres - Google Patents

Composition de résine époxy, pré-imprégné, et matériau composite renforcé par fibres Download PDF

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Publication number
WO2014142024A1
WO2014142024A1 PCT/JP2014/055952 JP2014055952W WO2014142024A1 WO 2014142024 A1 WO2014142024 A1 WO 2014142024A1 JP 2014055952 W JP2014055952 W JP 2014055952W WO 2014142024 A1 WO2014142024 A1 WO 2014142024A1
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epoxy resin
resin composition
mass
block copolymer
polymer
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PCT/JP2014/055952
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English (en)
Japanese (ja)
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野村圭一郎
森岡信博
小林定之
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東レ株式会社
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Priority to KR1020157026669A priority Critical patent/KR20150128755A/ko
Priority to CN201480013829.3A priority patent/CN105008456B/zh
Priority to EP14763086.7A priority patent/EP2975088A4/fr
Priority to JP2014513811A priority patent/JP5765484B2/ja
Priority to US14/763,065 priority patent/US9783670B2/en
Publication of WO2014142024A1 publication Critical patent/WO2014142024A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Definitions

  • the present invention relates to an epoxy resin composition from which an epoxy resin cured product excellent in toughness and rigidity can be obtained, and a prepreg and a fiber-reinforced composite material using the same.
  • Fiber reinforced composite materials using carbon fibers, aramid fibers, etc. as reinforcing fibers make use of their high specific strength and specific modulus to make structural materials such as aircraft and automobiles, sports applications such as tennis rackets, golf shafts and fishing rods Widely used in general industrial applications.
  • a method for producing these fiber reinforced composite materials a method is often used in which a prepreg, which is a sheet-like intermediate material in which reinforcing fibers are impregnated with a matrix resin, is laminated and then cured.
  • the method using a prepreg has an advantage that a high-performance fiber-reinforced composite material can be easily obtained because the orientation of the reinforcing fibers can be strictly controlled and the degree of freedom in designing the laminated structure is high.
  • a thermosetting resin composition is mainly used from the viewpoint of heat resistance and productivity, and an epoxy resin composition is preferable from the viewpoint of mechanical properties such as adhesion to reinforcing fibers. Used.
  • Fiber reinforced composite materials using epoxy resin as a matrix resin exhibit excellent heat resistance and good mechanical properties, but have low impact resistance due to low elongation and toughness of epoxy resin compared to thermoplastic resins. There is a need for improvement.
  • Patent Documents 1 and 2 propose a method of blending the thermoplastic component.
  • Patent Documents 1 and 3 propose a method of alloying a (meth) acrylic block copolymer with respect to an epoxy resin. In this method, excellent toughness can be provided by forming a fine phase structure without coarsening the phase separation structure, but further improvement in toughness is required.
  • Patent Document 5 As a technique for further improving the balance between toughness and rigidity of the cured epoxy resin, there is a technique for forming a phase separation structure after the curing reaction by using an epoxy resin composition combined with an epoxy compound having a specific SP value ( Patent Document 5).
  • This method is a technology that can express the toughness and rigidity of the cured epoxy resin by forming a fine phase separation structure after curing, greatly improving the performance of the matrix resin of the conventional fiber reinforced composite material It can be said that this technology can be improved.
  • depending on the reaction conditions there is also a problem that the physical properties deteriorate due to the change of the phase separation structure.
  • An object of the present invention is to provide an epoxy resin composition from which an epoxy resin cured product and a fiber reinforced composite material excellent in toughness and rigidity can be obtained.
  • An epoxy resin composition comprising an epoxy compound (A), a block copolymer (B), and a curing agent (C), wherein the block copolymer (B) is a (meth) acrylic polymer.
  • a polymer block (a) comprising a polymer block (b) comprising an acrylic polymer different from the polymer block (a), and a cured resin obtained by curing the epoxy resin composition.
  • An epoxy resin composition that forms a microphase-separated structure.
  • the epoxy according to (1) wherein 0 ⁇ X / Y ⁇ 1.10 is satisfied when the half-value width X of the primary scattering peak and the maximum wave number Y of the peak in the small-angle X-ray scattering measurement of the resin cured product are satisfied.
  • Resin composition (3)
  • the microphase separation structure of the cured resin product is any one structure selected from the group consisting of a lamellar structure, a gyroid structure, a cylinder structure, and a sphere structure, according to (1) or (2) The epoxy resin composition as described.
  • the block copolymer (B) is an ABA type triblock copolymer, A is the polymer block (a), and B is the polymer block (b).
  • the ratio of glycidyl (meth) acrylate in the polymer block (a) constituting the block copolymer (B) is 50% by mass or more, and any one of (1) to (5)
  • the ratio of n-butyl acrylate in the polymer block (b) constituting the block copolymer (B) is 50% by mass or more, and any one of (1) to (6) Epoxy resin composition.
  • the curing agent (C) is a polyamine-based curing agent, and the ratio of the polymer block (a) in the block copolymer (B) is 40% by mass or more and 70% by mass or less.
  • the curing agent (C) is a dicyandiamide-based curing agent, and the ratio of the polymer block (a) in the block copolymer (B) is 5% by mass or more and 40% by mass or less.
  • Epoxy resin composition (12)
  • the curing agent (C) is an anionic / cationic polymerization curing agent, and the ratio of the polymer block (a) in the block copolymer (B) is 5% by mass or more and 30% by mass or less, (9 ) Epoxy resin composition.
  • a prepreg comprising the epoxy resin composition according to any one of (1) to (12) and a reinforcing fiber.
  • a fiber-reinforced composite material comprising a cured resin obtained by curing the epoxy resin composition according to any one of (1) to (12), and reinforcing fibers.
  • a highly ordered microphase separation structure is formed in a cured epoxy resin obtained by curing, and has a fine and regular phase separation structure, which is excellent.
  • An epoxy resin cured product and a fiber reinforced composite material having toughness and rigidity are obtained.
  • the epoxy resin composition of the present invention comprises an epoxy compound (A), a block copolymer (B), and a curing agent (C) as essential components, and the cured resin forms a microphase separation structure after curing.
  • the epoxy compound (A) is a component necessary for heat resistance and mechanical property expression. Specifically, an epoxy resin having a precursor such as a phenol, amine, carboxylic acid, or intramolecular unsaturated carbon is preferred.
  • Examples of glycidyl ether type epoxy resins that use phenols as precursors include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, epoxy resins having a biphenyl skeleton, phenol novolac type epoxy resins, and cresol novolak type epoxy resins. Resin, resorcinol type epoxy resin, epoxy resin having naphthalene skeleton, trisphenylmethane type epoxy resin, phenol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, diphenylfluorene type epoxy resin and isomers and alkyl substitution of these epoxy resins And halogen-substituted products. Moreover, an epoxy resin obtained by modifying an epoxy resin having a phenol as a precursor with urethane or isocyanate is also included in this type.
  • bisphenol F type epoxy resin examples include Epicoat 806, Epicoat 807, Epicoat 1750, Epicoat 4004P, Epicoat 4007P, Epicoat 4009P (manufactured by Japan Epoxy Resin Co., Ltd.), Epicron 830 (Dainippon Ink Chemical Co., Ltd.) And Epototo YD-170, Epototo YD-175, Epototo YDF2001, Epototo YDF2004 (manufactured by Tohto Kasei Co., Ltd.) and the like. Moreover, YSLV-80XY (made by Nippon Steel Chemical Co., Ltd.) etc. is mentioned as a commercial item of the tetramethyl bisphenol F type epoxy resin which is an alkyl substitution product.
  • Examples of the bisphenol S type epoxy resin include Epicron EXA-1515 (manufactured by Dainippon Ink & Chemicals, Inc.).
  • epoxy resins having a biphenyl skeleton include Epicoat YX4000H, Epicoat YX4000, Epicoat YL6616, Epicoat YL6121H, Epicoat YL6640 (above, manufactured by Japan Epoxy Resin Co., Ltd.), NC-3000 (produced by Nippon Kayaku Co., Ltd.) Etc.
  • phenol novolac type epoxy resins include Epicoat 152, Epicoat 154 (manufactured by Japan Epoxy Resin Co., Ltd.), Epicron N-740, Epicron N-770, Epicron N-775 (above, Dainippon Ink & Chemicals, Inc.) Etc.).
  • cresol novolac type epoxy resins include Epicron N-660, Epicron N-665, Epicron N-670, Epicron N-673, Epicron N-695 (above, Dainippon Ink & Chemicals, Inc.), EOCN -1020, EOCN-102S, EOCN-104S (Nippon Kayaku Co., Ltd.).
  • Examples of commercially available resorcinol-type epoxy resins include “Denacol (registered trademark) (hereinafter, the registered trademark is omitted)” EX-201 (manufactured by Nagase ChemteX Corporation).
  • Examples of commercially available epoxy resins having a naphthalene skeleton include Epicron HP4032 (manufactured by Dainippon Ink and Chemicals, Inc.), NC-7000, NC-7300 (manufactured by Nippon Kayaku Co., Ltd.), and the like.
  • trisphenylmethane type epoxy resins examples include TMH-574 (manufactured by Sumitomo Chemical Co., Ltd.), Tactix 742 (manufactured by Huntsman Advanced Materials), and the like.
  • dicyclopentadiene-type epoxy resins include Epicron HP7200, Epicron HP7200L, Epicron HP7200H (manufactured by Dainippon Ink & Chemicals, Inc.), Tactix558 (manufactured by Huntsman Advanced Materials), XD-1000-1L XD-1000-2L (manufactured by Nippon Kayaku Co., Ltd.).
  • Examples of commercially available urethane and isocyanate-modified epoxy resins include AER4152 (produced by Asahi Kasei Epoxy Co., Ltd.) having an oxazolidone ring and ACR1348 (produced by Asahi Denka Co., Ltd.).
  • dimer acid-modified bisphenol A type epoxy resins examples include Epicoat 872 (manufactured by Japan Epoxy Resin Co., Ltd.).
  • glycidylamine-type epoxy resins that use amines as precursors include tetraglycidyldiaminodiphenylmethane, glycidyl compounds of xylenediamine, triglycidylaminophenol, glycidylaniline, and their positional isomers, alkyl-substituted products, and halogen-substituted products. It is done.
  • tetraglycidyldiaminodiphenylmethane is preferable as a resin for composite materials as an aircraft structural material because of its excellent heat resistance.
  • glycidyl anilines are preferable because a high elastic modulus is obtained.
  • Examples of commercially available glycidyl compounds of xylenediamine include TETRAD-X (manufactured by Mitsubishi Gas Chemical Company).
  • Examples of commercially available products of triglycidylaminophenol include Epicoat 630 (manufactured by Japan Epoxy Resin Co., Ltd.), Araldite MY0500, MY0510, MY0600 (manufactured by Huntsman Advanced Materials), ELM100 (manufactured by Sumitomo Chemical Co., Ltd.), and the like.
  • Examples of commercially available glycidyl anilines include GAN and GOT (manufactured by Nippon Kayaku Co., Ltd.).
  • Examples of the epoxy resin having a carboxylic acid as a precursor include glycidyl compounds of phthalic acid, glycidyl compounds of hexahydrophthalic acid, glycidyl compounds of dimer acid, and isomers thereof.
  • Examples of commercially available hexahydrophthalic acid diglycidyl ester include Epomic R540 (manufactured by Mitsui Chemicals), AK-601 (manufactured by Nippon Kayaku Co., Ltd.), and the like.
  • Examples of commercially available dimer acid diglycidyl ester include Epicoat 871 (manufactured by Japan Epoxy Resin Co., Ltd.) and Epototo YD-171 (manufactured by Toto Kasei Co., Ltd.).
  • Examples of the epoxy resin having an intramolecular unsaturated carbon as a precursor include an alicyclic epoxy resin.
  • Commercially available products include “Celoxide (registered trademark)” (hereinafter, the registered trademark is omitted) 2021, Celoxide 2080 (manufactured by Daicel Chemical Industries, Ltd.), CY183 (manufactured by Huntsman Advanced Materials). Is mentioned.
  • the epoxy resin composition of the present invention includes an epoxy compound (A) for the purpose of improving workability by adjusting the viscoelasticity of the composition, or for the purpose of improving the elastic modulus and heat resistance of the resulting cured resin.
  • Epoxy compounds other than) can be added within the range in which the effects of the present invention are not impaired. These may be added in combination of not only one type but also a plurality of types.
  • the curing agent (C) is not particularly limited as long as it cures the epoxy compound, but polyamine curing agents, dicyandiamide curing agents, anion / cation polymerization curing agents, acid anhydride curing agents, and the like. Can be mentioned.
  • the curing agent is a component necessary for curing the epoxy resin composition.
  • the polyamine-based curing agent is a curing agent having a plurality of primary amino groups in the molecule, and the epoxy resin composition is cured by an addition reaction between active hydrogen in the primary amino group and an epoxy group in the epoxy compound.
  • aromatic amines such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, and diethyltoluenediamine
  • aromatic amines such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, and diethyltoluenediamine
  • modified amines obtained by reacting compounds such as epoxy compounds, acrylonitrile, phenol and formaldehyde, thiourea with amine-based curing agents having active hydrogen such as aromatic amine-based curing agents and aliphatic amine-based curing agents System hardeners are also included in this category.
  • aromatic polyamine curing agents include Seika Cure S (manufactured by Wakayama Seika Kogyo Co., Ltd.), MDA-220 (manufactured by Mitsui Chemicals), “jER Cure (registered trademark)” W (Mitsubishi Chemical Corporation) ), And 3,3′-DAS (Mitsui Chemicals), Lonacure (registered trademark) M-DEA (Lonza), Lonacure (registered trademark) M-DIPA (Lonza) ), Lonacure (registered trademark) M-MIPA (manufactured by Lonza), Lonzacure (registered trademark) DETDA 80 (manufactured by Lonza), and the like.
  • the blending amount thereof is 0.5 to 1.5 with respect to the epoxy compound (A) in the epoxy resin composition from the viewpoint of heat resistance and mechanical properties. Equivalents are preferable, and 0.8 to 1.2 equivalents are more preferable. If it is less than 0.5 equivalent, the curing reaction may not proceed. When it exceeds 1.5 equivalents, the cured resin obtained by curing the epoxy resin composition may not form a microphase-separated structure, and as a result, the mechanical properties may deteriorate. It is preferable to blend the polyamine curing agent into the resin as a powder from the viewpoint of storage stability at room temperature.
  • the dicyandiamide-based curing agent In the dicyandiamide-based curing agent, four active hydrogens undergo an addition reaction with the epoxy group in the epoxy compound, and the reaction between the cyano group and the secondary hydroxyl group of the opened epoxy group. The cyano group and the epoxy group have an oxazoline ring. The epoxy resin composition is cured by the reaction to be formed.
  • the dicyandiamide-based curing agent includes not only dicyandiamide but also dicyandiamide derivatives in which various compounds such as an epoxy resin, a vinyl compound, and an acrylic compound are combined with dicyandiamide.
  • Examples of commercially available dicyandiamide include DICY-7 and DICY-15 (above, Japan Epoxy Resin Co., Ltd.).
  • the blending amount is 0.3 to 1.5 with respect to the epoxy compound (A) in the epoxy resin composition from the viewpoint of heat resistance and mechanical properties. It is preferably an equivalent, and more preferably 0.5 to 1.0 equivalent. If it is less than 0.3 equivalent, the curing reaction may not proceed. When it exceeds 1.5 equivalents, the cured resin obtained by curing the epoxy resin composition may not form a microphase-separated structure, and as a result, the mechanical properties may deteriorate. It is preferable to blend dicyandiamide or a derivative thereof into the resin as a powder from the viewpoint of storage stability at room temperature.
  • diandiamide When dicyandiamide is used as the curing agent (C), diandiamide may be used alone or in combination with a dicyandiamide curing catalyst or other epoxy resin curing agent.
  • a dicyandiamide curing catalyst include ureas, imidazoles, and Lewis acid catalysts.
  • the epoxy resin curing agent include an aromatic amine curing agent, an alicyclic amine curing agent, and an acid anhydride curing agent.
  • commercially available ureas include DCMU99 (manufactured by Hodogaya Chemical Co., Ltd.), Omicure 24, Omicure 52, and Omicure 94 (above CVC Specialty Chemicals, Inc.).
  • Lewis acid catalysts include boron trifluoride / piperidine complex, boron trifluoride / monoethylamine complex, boron trifluoride / triethanolamine complex, boron trichloride / octylamine complex, etc. Is mentioned.
  • the blending amount thereof is 0.5 to 5.0 parts by mass with respect to 100 parts by mass of the epoxy compound (A) in the epoxy resin composition from the viewpoint of heat resistance and mechanical properties.
  • the amount is 1.0 to 3.0 parts by mass.
  • the curing agent works as a catalyst for anionic polymerization / cationic polymerization, and the epoxy group in the epoxy compound is self-polymerized to cure the epoxy resin composition.
  • anionic polymerization type curing agents imidazoles such as 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole and their derivatives; adipic acid hydrazide, naphthalenecarboxylic acid hydrazide, etc.
  • carboxylic acid hydrazide derivatives such as N, N-dimethylaniline, N, N-dimethylbenzylamine, 2,4,6-tris (dimethylaminomethyl) phenol.
  • tertiary amines such as N, N-dimethylaniline, N, N-dimethylbenzylamine, 2,4,6-tris (dimethylaminomethyl) phenol.
  • the cationic polymerization curing agent include onium salt curing agents such as sulfonium salts, ammonium salts, and pyridinium salts, and aluminum complex composite curing agents.
  • imidazole or a derivative thereof is preferably used from the viewpoint of curing speed.
  • the blending amount thereof is 0.5 to 10 parts by mass with respect to 100 parts by mass of the epoxy compound (A) in the epoxy resin composition from the viewpoint of heat resistance and mechanical properties. preferable.
  • the amount is less than 0.5 parts by mass, the curing rate may be slow, and the curing reaction does not proceed sufficiently, which may adversely affect the mechanical properties.
  • it exceeds 10 mass parts although a cure rate will become quick, toughness may fall because a crosslinking density becomes high too much.
  • An acid anhydride-based curing agent is a curing agent having at least one carboxylic acid anhydride group in one molecule, and the epoxy resin composition is cured by a polycondensation reaction between the epoxy group in the epoxy compound and the carboxylic acid anhydride group. To do.
  • an acid anhydride having an aromatic ring such as phthalic anhydride but not having an alicyclic structure
  • an acid anhydride having neither an aromatic ring or an alicyclic structure such as succinic anhydride
  • hexahydro Phthalic anhydride methylhexahydrophthalic anhydride, methyldihydronadic anhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, 1,2,3,6-tetrahydrophthalic anhydride , Methyl-1,2,3,6-tetrahydrophthalic anhydride
  • nadic anhydride, methyl nadic anhydride bicyclo [2,2,2] oct-7-ene-2,3,5,6- Acid anhydrides having an alicyclic structure such as tetracarboxylic dianhydride and 4- (2,5-dioxotetrahydrofuran-3-yl) -3-methyl-1,2,5,6-tetra
  • the blending amount thereof is 0.5 to 1 with respect to the epoxy compound (A) in the epoxy resin composition from the viewpoint of heat resistance and mechanical properties.
  • 0.5 equivalent is preferable, and 0.8 to 1.2 equivalent is more preferable. If it is less than 0.5 equivalent, the curing reaction may not proceed. When it exceeds 1.5 equivalents, the cured resin obtained by curing the epoxy resin composition may not form a microphase-separated structure, and as a result, the mechanical properties may deteriorate.
  • the curing temperature and curing time for curing the epoxy resin composition of the present invention are not particularly limited, and can be appropriately selected depending on the curing agent and catalyst to be blended.
  • diaminodiphenylsulfone is used as the curing agent or catalyst
  • 2-ethyl-4-methylimidazole is obtained at a temperature of 180 ° C. for 2 hours
  • diaminodiphenylmethane is used, the temperature is 150 ° C. for 2 hours.
  • it is preferably cured at a temperature of 150 ° C. for 1 hour
  • dicyandiamide and DCMU it is preferably cured at a temperature of 135 ° C. for 2 hours.
  • the block copolymer (B) used in the present invention comprises (meth) acrylic (in this specification, methacryl and acrylic are collectively referred to as “(meth) acrylic”)-based polymer block (a) and polymer. It consists of a (meth) acrylic polymer block (b) different from the block (a).
  • the polymer block (a) is a block obtained by polymerizing a monomer selected from acrylic acid ester or methacrylic acid ester, and has a function of being compatible with the epoxy compound (A) after curing of the epoxy resin composition. Have.
  • the ratio of the monomer having a glycidyl group in the polymer block (a) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% or more. preferable.
  • the epoxy resin composition is cured by using a monomer having a glycidyl group for the polymer block (a)
  • the glycidyl group and the curing agent (C) are similar to the glycidyl group of the epoxy compound (A).
  • the epoxy compound (A) and the polymer block (a) are easily compatible with each other, so that a microphase separation structure is easily formed. As a result, the obtained cured resin can obtain desired mechanical properties.
  • the ratio of the monomer having a glycidyl group in the polymer block (a) is less than 50% by mass, the compatibility between the epoxy compound (A) and the block copolymer (B) is lowered, and the epoxy resin composition is reduced.
  • the cured resin obtained by curing may not form a microphase-separated structure, and sufficient mechanical properties may not be obtained.
  • Examples of the monomer having a glycidyl group include glycidyl (meth) acrylate, 2,3-epoxy-2-methylpropyl (meth) acrylate, and (3,4-epoxycyclohexyl) methyl (meth) acrylate ( Mention may be made of esters of (meth) acrylic acid with organic group-containing alcohols containing epoxy rings, and epoxy group-containing unsaturated compounds such as 4-vinyl-1-cyclohexene 1,2 epoxide. From the viewpoint of availability, glycidyl (meth) acrylate is preferably used.
  • the polymer block (a) is composed of monomers having a glycidyl group such as glycidyl methacrylate and glycidyl acrylate, as well as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate.
  • a glycidyl group such as glycidyl methacrylate and glycidyl acrylate, as well as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate.
  • Methacrylic acid such as n-pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, stearyl methacrylate
  • Alkyl esters may be included.
  • the alkyl ester is preferably an alkyl ester having 1 to 18 carbon atoms. These can be used alone or in combination of two or more.
  • the polymer block (b) is a polymer block obtained by polymerizing an acrylic monomer, which is different from the polymer block (a). After the epoxy resin composition is cured, the polymer block (b) is phase-separated. It has the function to do. Therefore, it is preferable that the ratio of the monomer which has a glycidyl group in a polymer block (b) is less than 50 mass%, and it is more preferable that the monomer which has a glycidyl group is not included.
  • Examples of the monomer contained in the polymer block (b) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2- (meth) acrylic acid 2- Mention may be made of (meth) acrylic acid alkyl esters such as ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) acrylic acid stearyl.
  • the alkyl ester is preferably an alkyl ester having 1 to 18 carbon atoms.
  • the polymer block (b) is more preferably composed of a monomer that forms a flexible polymer block from the viewpoint of improving mechanical properties of the cured product of the epoxy resin composition, particularly impact resistance and toughness.
  • Flexible polymer blocks include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, N-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth ) Stearyl acrylate.
  • the ratio of n-butyl acrylate in the polymer block (b) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more.
  • the ratio of n-butyl acrylate in the polymer block (b) is less than 50% by mass, the flexibility of n-butyl acrylate is not sufficiently exhibited, so that the resulting cured resin has impact resistance and toughness. Etc. may be low.
  • the ratio of the polymer block (a) in the block copolymer (B) varies depending on the type of the curing agent, but is preferably 5% by mass or more and 80% by mass or less in the block copolymer (B).
  • the ratio of the polymer block (a) is less than 5% by mass, the compatibility with the epoxy compound (A) is deteriorated, and a coarse phase separation structure may be formed after curing.
  • the ratio of a polymer block (a) exceeds 80 mass%, toughness may fall.
  • the ratio of the polymer block (a) in the block copolymer (B) is more preferably 40% by mass or more and 70% by mass or less.
  • the range of 40 mass% or more and 60 mass% or less is more preferable.
  • the ratio of the polymer block (a) is less than 40% by mass, the compatibility with the epoxy compound is deteriorated, and a coarse phase separation structure may be formed after curing.
  • the ratio of a polymer block (a) is 70 mass% or less, the hardened
  • the ratio of the polymer block (a) in the block copolymer (B) is preferably 5% by mass or more and 40% by mass or less. % To 30% by mass is more preferable.
  • the ratio of the polymer block (a) is less than 5% by mass, the compatibility with the epoxy compound is deteriorated, and a coarse phase separation structure may be formed after curing.
  • the ratio of a polymer block (a) is 40 mass% or less, the hardened
  • the ratio of the polymer block (a) in the block copolymer (B) is preferably 5% by mass or more and 30% by mass or less. The range of mass% or more and 20 mass% or less is more preferable.
  • the ratio of the polymer block (a) is less than 5% by mass, the compatibility with the epoxy compound is deteriorated, and a coarse phase separation structure may be formed after curing.
  • the ratio of a polymer block (a) is 30 mass% or less, the hardened
  • the ratio of the polymer block (a) in the block copolymer (B) can be calculated using 1 H-NMR measurement using deuterated chloroform as a solvent.
  • the molecular form of the block copolymer (B) may be any of a linear block copolymer, a branched block copolymer and a mixture thereof, but is linear in terms of cost and ease of polymerization. Block copolymers are preferred. Further, the linear block copolymer may have any structure, but from the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, the linear block copolymer may be a triblock copolymer. Particularly preferred. Furthermore, it is a triblock copolymer represented by ABA when the polymer block (a) is A and the polymer block (b) is B from the viewpoint of ease of handling during processing and physical properties of the composition. It is preferable.
  • the lower limit of the weight average molecular weight of the block copolymer (B) is preferably 10,000 or more, and more preferably 40,000 or more. When the weight average molecular weight is less than 10,000, the mechanical properties of the polymer block (b) may not be sufficiently exhibited, and the toughness may decrease.
  • the upper limit of the weight average molecular weight of the block copolymer (B) is preferably 400,000 or less, more preferably 200,000 or less, and further preferably 100,000 or less. When the weight average molecular weight exceeds 400,000, the handleability of the block copolymer itself may be poor, and when the epoxy resin composition is used, the viscosity increases, which may cause problems during molding.
  • the block copolymer (B) preferably has a molecular weight distribution (Mw / Mn), which is a ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn), of 1.50 or less, and is 1.20 or less. It is more preferable. If the molecular weight distribution is large and the molecular chain length is not uniform, the cured product of the epoxy resin composition may not form a microphase separation structure due to a decrease in molecular uniformity, resulting in a decrease in mechanical properties. is there.
  • requiring by converting into molecular weight using the retention time of the calibration sample of polymethyl methacrylate using gel permeation chromatography (GPC) can be used.
  • the content ratio of the block copolymer (B) in the epoxy resin composition of the present invention is preferably 10% by mass or more. If the content ratio is less than 10% by mass, the microphase separation structure may not be formed because the ratio of the polymer block (b) constituting the phase (II) in the microphase separation structure is too small. .
  • the content ratio of the block copolymer (B) in the epoxy resin composition is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by weight or less. preferable. When the content ratio exceeds 50% by mass, there may be a problem during molding, such as when the epoxy resin composition is used, the viscosity becomes too high, resulting in poor handling of the resin.
  • the epoxy resin composition of the present invention is characterized in that a cured resin product after curing forms a microphase separation structure.
  • the microphase separation structure is a phase separation structure formed through microphase separation.
  • Microphase separation refers to a periodic block of about the size of a molecular chain so that a block copolymer in which two or more kinds of inherently incompatible polymers are covalently bonded to each other minimizes the interfacial area. This is a phase separation mode in which a simple interface is spontaneously formed and phase-separated into a phase (I) and a phase (II) at the molecular level.
  • the components constituting the (I) phase and the (II) phase are components constituting the block copolymer, but may contain other components that are compatible with the (I) phase or the (II) phase.
  • the microphase-separated structure is characterized by being highly ordered, whereby an epoxy resin cured product and a fiber-reinforced composite material having an excellent balance between toughness and rigidity can be obtained.
  • the epoxy compound (A), the block copolymer (B) and the curing agent (C) are compatible before the curing reaction, and after the curing reaction, the (I) phase and ( II) It is preferable to perform microphase separation into phases.
  • the phase (I) is preferably composed of a phase in which the cured product of the epoxy compound (A) and the polymer block (a) constituting the block copolymer (B) are compatible, and (II)
  • the phase is preferably composed of a polymer block (b) constituting the block copolymer (B).
  • the order of the microphase separation structure can be confirmed by scattering measurement including, for example, small angle X-ray scattering measurement and neutron scattering measurement.
  • scattering measurement it can be said that the narrower the peak of the angular distribution profile of the scattering intensity derived from the phase structure is, the more ordered it is.
  • the microphase-separated structure of the cured product obtained by curing the epoxy resin composition of the present invention can be confirmed by the angle distribution profile of the scattering intensity of the small angle X-ray scattering measurement.
  • the small-angle X-ray scattering measurement it is preferable that 0 ⁇ X / Y ⁇ 1.10 is satisfied, where X is the half width of the primary scattering peak derived from the microphase-separated structure and Y is the maximum wave number of the peak. It is more preferable that ⁇ X / Y ⁇ 1.05.
  • a secondary or higher scattering peak derived from the microphase separation structure is detected. Detecting a secondary or higher scattering peak indicates that the phase separation structure is very highly ordered.
  • the microphase separation structure is generally divided into a lamellar structure, a gyroidal structure, a cylinder structure, and a sphere structure.
  • the microphase separation structure of the cured product of the epoxy resin composition of the present invention is preferably any structure selected from the group consisting of these.
  • the method for confirming the microphase separation structure includes observation with a transmission electron microscope or observation with a scanning electron microscope of a cross section of the cured resin.
  • the measurement sample may be stained with osmium or the like, if necessary. Dyeing can be performed by a usual method.
  • the value of the scattering vector of the n-th scattering peak is q n
  • the value of q n / q 1 The form of the microphase separation structure of the resin cured product can be estimated. lamellar structure when the value of q n / q 1 is 1, 2, 3, 1, 3 0.5, cylinder structure in the case of 2,7 0.5., 1,2 0.5 In the case of 3 0.5 ..., It can be estimated as a sphere structure.
  • the structural period of the micro phase separation structure formed by the cured product of the epoxy resin composition is preferably 10 nm or more, and more preferably 20 nm or more. If the structural period is less than 10 nm, the difference from the compatible state is difficult to understand, and the effect of the microphase separation structure may not be exhibited. Further, the structural period is preferably 200 nm or less, more preferably 150 nm or less, and further preferably 100 nm or less. When the structural period exceeds 200 nm, the phase separation structure becomes too large, and it becomes difficult to express excellent physical properties.
  • the structural period of such a microphase-separated structure can be measured by the small angle X-ray scattering measurement, transmission electron microscope observation, or scanning electron microscope observation.
  • ⁇ m ( ⁇ / 2) / sin ( ⁇ m / 2) using the scattering angle ⁇ m given by the obtained scattering peak and the wavelength ⁇ of the scattered light in the scatterer.
  • the structural period ⁇ m can be obtained.
  • the structural period ⁇ m can be obtained from k.
  • the epoxy resin composition of the present invention can be blended with a thermoplastic resin soluble in an epoxy compound, organic particles such as rubber particles and thermoplastic resin particles, and the like within a range not impairing the object of the present invention.
  • thermoplastic resin soluble in the epoxy compound a thermoplastic resin having a hydrogen bonding functional group that can be expected to improve the adhesion between the epoxy resin composition and the reinforcing fiber is preferably used.
  • the hydrogen bondable functional group include an alcoholic hydroxyl group, an amide bond, a sulfonyl group, and a carboxyl group.
  • thermoplastic resin having an alcoholic hydroxyl group examples include polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, polyvinyl alcohol, and phenoxy resins.
  • thermoplastic resin having an amide bond examples include polyamide, polyimide, polyamideimide, and polyvinylpyrrolidone.
  • thermoplastic resin having a sulfonyl group examples include polysulfone.
  • Polyamide, polyimide and polysulfone may have a functional group such as an ether bond and a carbonyl group in the main chain.
  • the polyamide may have a substituent on the nitrogen atom of the amide group.
  • thermoplastic resin having a carboxyl group examples include polyester, polyamide, and polyamideimide.
  • thermoplastic resins that are soluble in epoxy compounds and have hydrogen-bonding functional groups include Denkabutyral as a polyvinyl acetal resin and “Denkapoval (registered trademark)” as a polyvinyl alcohol resin (Electrochemical Industry Co., Ltd.) ), “Vinylec (registered trademark)” (manufactured by Chisso Corporation), “Macromelt (registered trademark)” (manufactured by Henkel Co., Ltd.), “Amilan (registered trademark)” CM4000 (manufactured by Toray Industries, Inc.) as a polyamide resin "Ultem (registered trademark)” (manufactured by Subic Innovative Plastics), “Aurum (registered trademark)” (manufactured by Mitsui Chemicals), “Vespel (registered trademark)” (manufactured by DuPont) as a polyimide "Victrex (registered trademark)”
  • the acrylic resin has high compatibility with the epoxy resin and is preferably used for controlling the viscoelasticity.
  • Commercially available acrylic resins include “Dianar (registered trademark)” BR series (Mitsubishi Rayon Co., Ltd.), “Matsumoto Microsphere (registered trademark)” M, M100, M500 (Matsumoto Yushi Seiyaku Co., Ltd.) ) And the like.
  • cross-linked rubber particles, and core-shell rubber particles obtained by graft polymerization of a different polymer on the surface of the cross-linked rubber particles are preferably used from the viewpoint of handleability and the like.
  • Examples of commercially available core-shell rubber particles include “Paraloid (registered trademark)” EXL-2655, EXL-2611, and EXL-3387 (produced by Rohm and Haas Co., Ltd.) made of a butadiene / alkyl methacrylate / styrene copolymer.
  • thermoplastic resin particles polyamide particles or polyimide particles are preferably used.
  • polyamide particles SP-500 (manufactured by Toray Industries, Inc.), “Orgazol (registered trademark)” (manufactured by Arkema Co., Ltd.) and the like can be used.
  • additives may be added to the epoxy resin composition of the present invention as long as the object of the present invention is not impaired.
  • these other additives include talc, kaolin, mica, clay, bentonite, sericite, basic magnesium carbonate, aluminum hydroxide, glass flake, glass fiber, carbon fiber, asbestos fiber, rock wool, calcium carbonate, Silica sand, wollastonite, barium sulfate, glass beads, titanium oxide and other reinforcing or non-plate-like fillers; or antioxidants (phosphorous, sulfur, etc.); UV absorbers; heat stabilizers (hindered phenols) Lubricants; Release agents; Antistatic agents; Antiblocking agents; Colorants including dyes and pigments; Flame retardants (halogen-based, phosphorus-based, etc.); Flame retardant aids (antimony compounds typified by antimony trioxide) , Zirconium oxide, molybdenum oxide, etc.); foaming agent; coupling agent (epoxy group, amino group
  • a prepreg can be obtained by combining the epoxy resin composition of the present invention and reinforcing fibers.
  • the reinforcing fiber used in the present invention is not particularly limited, and glass fiber, carbon fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like are used. Two or more of these fibers may be mixed and used. Among these, it is preferable to use carbon fibers from which a lightweight and highly rigid fiber-reinforced composite material can be obtained. Of these, carbon fibers having a tensile modulus of 230 to 800 GPa are preferably used. When such a high elastic modulus carbon fiber is combined with the epoxy resin composition of the present invention, the effects of the present invention are particularly prominent, and good impact resistance tends to be obtained.
  • the form of the reinforcing fiber is not particularly limited, and for example, long fiber, tow, woven fabric, mat, knit, braid, short fiber, etc. aligned in one direction are used.
  • the term “long fiber” as used herein refers to a single fiber or fiber bundle that is substantially continuous by 10 mm or more.
  • a short fiber is a fiber bundle cut to a length of less than 10 mm.
  • an array in which reinforcing fiber bundles are aligned in a single direction is most suitable.
  • a prepreg can be produced by impregnating a reinforcing fiber with an epoxy resin composition.
  • the impregnation method include a wet method and a hot melt method (dry method).
  • the reinforcing fiber is pulled up and the solvent is evaporated from the reinforcing fiber using an oven or the like. This is a method of impregnating a reinforcing fiber.
  • the hot melt method is a method in which a reinforcing fiber is impregnated directly with an epoxy resin composition whose viscosity is reduced by heating, or a film in which an epoxy resin composition is coated on a release paper is prepared, and then both sides of the reinforcing fiber Alternatively, it is a method of impregnating a reinforcing fiber with a resin by overlapping the film from one side and heating and pressing. In particular, since there is no solvent remaining in the prepreg, it is preferable to use a hot melt method.
  • the amount of reinforcing fibers per unit area of the prepreg is preferably 70 to 200 g / m 2 .
  • the fiber content in the prepreg is preferably 60 to 90% by mass, more preferably 65 to 85% by mass, and further preferably 70 to 80% by mass.
  • the fiber content is less than 60% by mass, the ratio of the resin is too large, so that the advantage of the fiber reinforced composite material having excellent specific strength and specific elastic modulus cannot be obtained, and the calorific value upon curing of the epoxy resin composition is not obtained. May be too high. Moreover, since the impregnation defect of resin will be produced when a fiber content rate exceeds 90 mass%, there exists a possibility that the fiber reinforced composite material obtained may be a thing with many voids.
  • a fiber-reinforced composite material can be obtained by curing the above prepreg. Moreover, a fiber-reinforced composite material can also be obtained by combining and curing the epoxy resin composition of the present invention with reinforcing fibers without going through an intermediate such as a prepreg.
  • the production method of the fiber reinforced composite material is not particularly limited, but the prepreg lamination molding method, the resin transfer molding method, the resin film infusion method, the hand layup method, the sheet molding compound method, the filament winding method, and the pultrusion method. Can be used.
  • the resin transfer molding method is a method in which a reinforcing fiber base material is directly impregnated with a liquid epoxy resin composition and cured. Since this method does not go through an intermediate such as a prepreg, it has the potential to reduce the molding cost and can be suitably used for structural materials such as spacecraft, aircraft, railway vehicles, automobiles, and ships.
  • the filament winding method one to several tens of rovings are arranged, and while impregnating the epoxy resin composition, tension is applied and a rotating mold (mandrel) is formed at a predetermined angle until it reaches a predetermined thickness. It is a method of demolding after winding and curing of the epoxy resin composition.
  • the reinforcing fibers are continuously passed through an impregnation tank filled with a liquid epoxy resin composition, and the reinforcing fibers impregnated with the epoxy resin composition are passed through a squeeze die and a heating mold by a tension machine.
  • This is a molding method in which molding and curing are performed while continuously drawing. Since this method has an advantage that a fiber reinforced composite material can be continuously formed, it is used for manufacturing reinforced fiber plastics (FRP) such as fishing rods, rods, pipes, sheets, antennas, and building structures.
  • FRP reinforced fiber plastics
  • the prepreg laminate molding method is a method in which after shaping and / or laminating a prepreg, the epoxy resin composition is heated and cured while applying pressure to the shaped product and / or the laminate.
  • a press molding method as a method of applying heat and pressure, a press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method, an internal pressure molding method, or the like can be appropriately used.
  • the autoclave molding method is a method in which a prepreg is laminated on a tool plate having a predetermined shape, covered with a bagging film, and cured by pressure and heating while degassing the inside of the laminate.
  • the fiber orientation can be precisely controlled, and the generation of voids is small, so that a molded article having excellent mechanical properties and high quality can be obtained.
  • the pressure applied during molding is preferably 3 to 20 kg / cm 2 .
  • the molding temperature is preferably in the range of 90 to 200 ° C.
  • the wrapping tape method is a method of forming a tubular body made of a fiber reinforced composite material by winding a prepreg around a mandrel or the like.
  • This method is a preferable method when producing rod-shaped bodies such as golf shafts and fishing rods. More specifically, the prepreg is wound around a mandrel, and a wrapping tape made of a thermoplastic film is wound outside the wound prepreg for fixing and applying pressure, and tension is applied to the prepreg.
  • the resin is heated and cured in an oven, and then the mandrel is removed to obtain a tubular body.
  • the tension applied to the prepreg by the wrapping tape is preferably 2.0 to 8.0 kgf.
  • the molding temperature is preferably in the range of 80 to 200 ° C.
  • the internal pressure molding method is to set a preform in which a prepreg is wound on an internal pressure applying body such as a tube made of a thermoplastic resin in a mold, and then introduce a high pressure gas into the internal pressure applying body to apply pressure. At the same time, the mold is heated and molded.
  • This method is preferably used when molding a complicated shape such as a golf shaft, a bad, a racket such as tennis or badminton.
  • the pressure applied during molding is preferably 5 to 20 kg / cm 2 .
  • the molding temperature is preferably in the range of room temperature to 200 ° C, more preferably in the range of 80 to 180 ° C.
  • the prepreg laminate molding method is preferable because the obtained fiber-reinforced composite material is excellent in rigidity and strength.
  • the fiber reinforced composite material using the cured product of the epoxy resin composition of the present invention as a matrix resin is preferably used for sports applications, general industrial applications, and aerospace applications. More specifically, in sports applications, it is preferably used for golf shafts, fishing rods, tennis or badminton racket applications, stick applications such as hockey, and ski pole applications. In addition, in general industrial applications, structural materials for moving bodies such as automobiles, bicycles, ships and railway vehicles, drive shafts, leaf springs, windmill blades, pressure vessels, flywheels, paper rollers, roofing materials, cables, and repair reinforcement materials Etc. are preferably used.
  • Example demonstrates the epoxy resin composition of this invention further in detail, this invention is not limited by these examples.
  • the following resin raw materials were used.
  • ⁇ Curing agent> ⁇ 4-Methyl-2-ethylimidazole (manufactured by Wako Pure Chemical Industries) -Dicyandiamide (DICY7, manufactured by Mitsubishi Chemical). ⁇ 3,3'-Diaminodiphenylsulfone ⁇ Curing Accelerator> • 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU99, manufactured by Hodogaya Chemical Co., Ltd.).
  • Resin preparation and various physical properties were measured by the following methods.
  • the physical properties were measured in an environment with a temperature of 23 ° C. and a relative humidity of 50% unless otherwise specified.
  • the obtained block copolymer is an ABA triblock copolymer, where A is the polymer block (a) and B is the polymer block (b), and the polymer block ( The ratio of glycidyl methacrylate in a) was 100% by mass, and the ratio of butyl acrylate in the polymer block (b) was also 100% by mass.
  • the solution was heated under reduced pressure at 100 ° C. for 1 hour to remove the solvent and residual monomer, thereby obtaining an n-butyl acrylate polymer (PBA3).
  • PBA3 n-butyl acrylate polymer
  • the obtained precipitate was dissolved in acetone, and the metal component was removed through an activated alumina column. Then, the block copolymer (BCP1) was obtained by removing acetone from a solution at room temperature and pressure reduction using a rotary evaporator, and making it vacuum-dry.
  • the molecular weight of the polymer obtained using GPC was measured as shown in (3) below, the weight average molecular weight was 61,900 and the molecular weight distribution was 1.27.
  • the ratio of the glycidyl methacrylate polymer was calculated using NMR as shown in (4) below, the ratio of the glycidyl methacrylate polymer to the entire copolymer was 10% by mass.
  • the obtained precipitate was dissolved in acetone, and the metal component was removed through an activated alumina column. Then, the block copolymer (BCP5) was obtained by removing acetone from a solution at room temperature and pressure reduction using a rotary evaporator, and making it vacuum-dry.
  • the molecular weight of the polymer obtained using GPC was measured as shown in (3) below, the weight average molecular weight was 87, 200, and the molecular weight distribution was 1.30.
  • the ratio of the glycidyl methacrylate polymer was calculated using NMR as shown in (4) below, the ratio of the glycidyl methacrylate polymer to the entire copolymer was 13% by mass.
  • the obtained precipitate was dissolved in acetone, and the metal component was removed through an activated alumina column. Then, the block copolymer (BCP7) was obtained by removing acetone from a solution at normal temperature and pressure reduction using a rotary evaporator, and making it vacuum-dry.
  • the molecular weight of the polymer obtained using GPC was measured as shown in (3) below, the weight average molecular weight was 157,500 and the molecular weight distribution was 1.49.
  • the ratio of the glycidyl methacrylate polymer was calculated using NMR as shown in (4) below, the ratio of the glycidyl methacrylate polymer to the entire copolymer was 15% by mass.
  • the obtained precipitate was dissolved in acetone, and the metal component was removed through an activated alumina column. Then, the block copolymer (BCP9) was obtained by removing acetone from a solution at room temperature and pressure reduction using a rotary evaporator, and making it vacuum-dry.
  • the molecular weight of the polymer obtained using GPC was measured as shown in (3) below, the weight average molecular weight was 60,500 and the molecular weight distribution was 1.46.
  • the ratio of the glycidyl methacrylate polymer was calculated using NMR as shown in (4) below, the ratio of the glycidyl methacrylate polymer to the entire copolymer was 66% by mass.
  • the obtained precipitate was dissolved in acetone, and the metal component was removed through an activated alumina column. Then, the block copolymer (BCP10) was obtained by removing acetone from a solution at room temperature and pressure reduction using a rotary evaporator, and making it vacuum-dry.
  • the molecular weight of the polymer obtained using GPC was measured as shown in (3) below, the weight average molecular weight was 40,800 and the molecular weight distribution was 1.48.
  • the ratio of the glycidyl methacrylate polymer was calculated using NMR as shown in (4) below, the ratio of the glycidyl methacrylate polymer to the entire copolymer was 47% by mass.
  • the obtained precipitate was dissolved in acetone, and the metal component was removed through an activated alumina column. Then, the block copolymer (BCP11) was obtained by removing acetone from a solution at normal temperature and pressure reduction using a rotary evaporator, and making it vacuum-dry.
  • the molecular weight of the polymer obtained using GPC was measured as shown in (3) below, the weight average molecular weight was 33,200 and the molecular weight distribution was 1.44.
  • the ratio of the glycidyl methacrylate polymer was calculated using NMR as shown in (4) below, the ratio of the glycidyl methacrylate polymer to the entire copolymer was 66% by mass.
  • the weight average molecular weight and molecular weight distribution were calculated using gel permeation chromatography (GPC).
  • the weight average molecular weight and molecular weight distribution were measured using Shimadzu GPC system (LC-20AD, CBM-20A, RID-10A, SPD-M20A, CTO-20A, SIL-20A HT , DGU-20A 3 ) as a solvent.
  • Shimadzu GPC system LC-20AD, CBM-20A, RID-10A, SPD-M20A, CTO-20A, SIL-20A HT , DGU-20A 3
  • Tetrahydrofuran, two "Shodex (registered trademark)” 80M (made by Showa Denko) and one "Shodex (registered trademark)” 802 (made by Showa Denko) are used in the column, and RI (differential refractive index) is used as a detector.
  • a detector was used. 0.3 ⁇ L of the sample was injected, and the retention time of the sample measured at a flow rate of 1 mL / min was calculated by converting it to molecular weight using the retention time of the calibration sample for polymethylmethacrylic acid. Furthermore, molecular weight distribution (Mn / Mw) was calculated
  • Ratio measurement of polymer block The ratio of each polymer block to the whole copolymer was calculated by 1 H-NMR measurement using deuterated chloroform as a solvent.
  • the peak area derived from the glycidyl group of the glycidyl methacrylate polymer and the peak area derived from the alkyl group of the butyl acrylate polymer was calculated from the ratio.
  • the X-ray used was measured with a line light source having a wavelength of 1.54 angstroms and an SAXS imaging plate as a detector for an integration time of 3 minutes.
  • the obtained two-dimensional image was integrated for 10 pixels in the direction perpendicular to the line ray using the analysis software “SAXSquant 3.80”.
  • SAXSquant 3.80 From the obtained one-dimensional scattering profile, the presence or absence of a peak is confirmed.
  • the scattering angle ⁇ m giving the primary scattering peak and the wavelength ⁇ of the scattered light in the scatterer are used.
  • the value of X / Y was calculated, where X is the half width of the primary scattering peak and Y is the maximum wave number of the peak.
  • Electron microscope observation of cured product (measurement of presence or absence of microphase separation structure)
  • the prepared cured resin was dyed and then cut into thin sections, and a transmission electron image was obtained at an appropriate magnification using a transmission electron microscope under the following conditions to confirm the presence or absence of a microphase separation structure.
  • As the staining agent OsO 4 and RuO 4 were properly used according to the resin composition so that the morphology was sufficiently contrasted.
  • the appropriate magnification is 50,000 times when the structural period obtained by small-angle X-ray scattering is 1 nm or more and less than 10 nm, 20,000 times when the structural period is 10 nm or more and less than 100 nm, and the structural period is 100 nm.
  • the 90 ° bending strength of the fiber reinforced composite material was measured as an index of adhesion between the epoxy resin composition and the reinforced fiber.
  • the unidirectional laminate produced in the above (12) was cut out to have a thickness of 2 mm, a width of 15 mm, and a length of 60 mm.
  • Instron universal testing machine Instron
  • measurement was performed under the conditions of a crosshead speed of 1.0 mm / min, a span of 40 mm, an indenter diameter of 10 mm, and a fulcrum diameter of 4 mm.
  • 90 ° bending strength and bending breaking elongation was measured.
  • the bending strength and bending breaking elongation which were obtained were converted into Vf60%.
  • Examples 1 to 9 As shown in Table 1, an epoxy compound, a block copolymer and a curing agent were blended by the method described in Production Example 1 and Production Example 4 to produce an epoxy resin composition and a cured product thereof. From the small-angle X-ray scattering measurement and the electron microscope observation, it was revealed that the cured product formed a cylindrical microphase separation structure. As a result of various physical property measurements, the obtained cured product had good bending elastic modulus, bending rupture elongation, and toughness.
  • Example 10 to 13 As shown in Table 2, an epoxy compound, a block copolymer and a curing agent were blended by the method described in Production Example 2 and Production Example 5 to produce an epoxy resin composition and a cured product thereof. From the small-angle X-ray scattering measurement and the electron microscope observation, it was revealed that the cured product formed a cylindrical microphase separation structure. As a result of various physical property measurements, the obtained cured product had good bending elastic modulus, bending rupture elongation, and toughness. Furthermore, the heat resistance was also good.
  • Examples 14 to 19 As shown in Table 2, an epoxy compound, a block copolymer and a curing agent were blended by the method described in Production Example 3 and Production Example 6 to produce an epoxy resin composition and a cured product thereof. From the small-angle X-ray scattering measurement and the electron microscope observation, it was revealed that the cured product formed a cylindrical microphase separation structure. As a result of various physical property measurements, the obtained cured product had good bending elastic modulus, bending rupture elongation, and toughness.
  • Example 20 to 23 As shown in Table 5, an epoxy resin composition was produced by the method described in Production Example 2, and a unidirectional laminate of fiber-reinforced composite material was produced by the method (12). When 0 ° and 90 ° bending tests were performed, the bending strength and the bending elongation at break were both good.
  • the fiber reinforced composite material using the cured product of the epoxy resin composition of the present invention as a matrix resin is preferably used for sports applications, general industrial applications, and aerospace applications. More specifically, in sports applications, it is preferably used for golf shafts, fishing rods, tennis and badminton racket applications, stick applications such as hockey, and ski pole applications. In addition, in general industrial applications, structural materials for moving bodies such as automobiles, bicycles, ships and railway vehicles, drive shafts, leaf springs, windmill blades, pressure vessels, flywheels, paper rollers, roofing materials, cables, and repair reinforcement materials Etc. are preferably used.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Epoxy Resins (AREA)

Abstract

Composition de résine époxy selon la présente invention comprenant un composé époxy (A), un copolymère séquencé (B) et un agent durcisseur (C), le copolymère séquencé (B) étant constitué d'une séquence polymère (a) comprenant un polymère (méth)acrylique et d'une séquence polymère (b) comprenant un polymère acrylique qui est différent de la séquence polymère (a), ladite composition de résine époxy ayant une propriété telle qu'un produit de résine durci obtenu par durcissement de ladite composition de résine époxy forme une structure séparée par des microphases. Un produit durci à base de la composition de résine époxy selon l'invention forme une structure à phases très ordonnées, et ayant par conséquent une excellente ténacité et rigidité.
PCT/JP2014/055952 2013-03-11 2014-03-07 Composition de résine époxy, pré-imprégné, et matériau composite renforcé par fibres WO2014142024A1 (fr)

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CN201480013829.3A CN105008456B (zh) 2013-03-11 2014-03-07 环氧树脂组合物、预浸料坯及纤维增强复合材料
EP14763086.7A EP2975088A4 (fr) 2013-03-11 2014-03-07 Composition de résine époxy, pré-imprégné, et matériau composite renforcé par fibres
JP2014513811A JP5765484B2 (ja) 2013-03-11 2014-03-07 エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料
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TW201437280A (zh) 2014-10-01
EP2975088A4 (fr) 2017-02-22
TWI602875B (zh) 2017-10-21
JPWO2014142024A1 (ja) 2017-02-16
CN105008456A (zh) 2015-10-28
JP5765484B2 (ja) 2015-08-19
US9783670B2 (en) 2017-10-10

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